1,4-Dioxane → HCID 86686381, compound

HRID 1043951Notes

Reaction equation

HRID 1043951 reaction equation
[O:1]1[CH2:7][CH:6]([N:8]2[C:12]([C:13]3[CH:18]=[CH:17][C:16](B4OC(C)(C)C(C)(C)O4)=[CH:15][C:14]=3[N+:28]([O-:30])=[O:29])=[C:11]([C:31]([O:33][CH2:34][CH3:35])=[O:32])[CH:10]=[N:9]2)[CH2:5][O:4][CH2:3][CH2:2]1.O1[CH2:41][CH2:40][O:39][CH2:38]C1>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>[O:4]1[CH2:5][CH:6]([N:8]2[C:12]([C:13]3[CH:18]=[CH:17][C:16]([C:41]4[C:40]([O:39][CH3:38])=[N:8][C:12]([CH3:11])=[CH:13][C:14]=4[CH3:15])=[CH:15][C:14]=3[N+:28]([O-:30])=[O:29])=[C:11]([C:31]([O:33][CH2:34][CH3:35])=[O:32])[CH:10]=[N:9]2)[CH2:7][O:1][CH2:2][CH2:3]1

Participants

4

Reactant 2

HCID 312751,4-DioxaneHCID 86686382HCID 86686382, compound

Product 1

HCID 86686381HCID 86686381, compound

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
100 °C

Procedure

Water (0.3 mL), 3-bromo-2-methoxy-4,6-dimethylpyridine (32.5 mg) obtained in Preparation Example 26, Pd(PPh3)4 (7.2 mg) and cesium carbonate (122 mg) were added to a solution of ethyl 1-(1,4-dioxepan-6-yl)-5-[2-nitro-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1H-pyrazole-4-carboxylate (61 mg) in 1,4-dioxane (1.2 mL), and the reaction mixture was stirred at 100° C. for 4 hours. Pd(PPh3)4 (7.2 mg) was added to the reaction mixture, and the reaction mixture was stirred at 100° C. for 1 hour and 10 minutes. The reaction mixture was returned to room temperature and partitioned by adding ethyl acetate and water, and the organic layer was separated. The resulting organic layer was sequentially washed with water and brine, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (ethyl acetate/n-heptane, 15 to 20%) to give the title compound (15 mg).

Workup

  1. stirringthe reaction mixture was stirred at 100° C. for 1 hour and 10 minutes
  2. customwas returned to room temperature
  3. custompartitioned
  4. additionby adding ethyl acetate and water
  5. customthe organic layer was separated
  6. washThe resulting organic layer was sequentially washed with water and brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated under reduced pressure
  10. customThe residue was purified by silica gel column chromatography (ethyl acetate/n-heptane, 15 to 20%)

Sources & evidence

ORD record
ord-d7caf20bb0e74fd8962605caec52831a
Source dataset
uspto-grants-2013_10
Patent number
US08563565B2

Reaction notes

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