2-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline → HCID 67364747, compound

HRID 245757Notes

Reaction equation

HRID 245757 reaction equation
[CH3:1][O:2][C:3]1[CH:9]=[C:8]([B:10]2[O:14][C:13]([CH3:16])([CH3:15])[C:12]([CH3:18])([CH3:17])[O:11]2)[CH:7]=[CH:6][C:4]=1[NH2:5].[Cl:19][C:20]1[CH:21]=[C:22]2[CH:28]=[C:27]([C:29](OC)=[O:30])[N:26]([CH3:33])[C:23]2=[N:24][CH:25]=1>O1CCCC1>[Cl:19][C:20]1[CH:21]=[C:22]2[CH:28]=[C:27]([C:29]([NH:5][C:4]3[CH:6]=[CH:7][C:8]([B:10]4[O:14][C:13]([CH3:16])([CH3:15])[C:12]([CH3:18])([CH3:17])[O:11]4)=[CH:9][C:3]=3[O:2][CH3:1])=[O:30])[N:26]([CH3:33])[C:23]2=[N:24][CH:25]=1

Participants

4

Reactant 2

HCID 177502072-Methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)anilineHCID 67363339HCID 67363339, compound

Product 1

HCID 67364747HCID 67364747, compoundYield 84%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Procedure

To 2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (2.073 g, 8.32 mmol) in tetrahydrofuran (dry) (20 ml) under a nitrogen atmosphere was added 2-Methylmagnesium chloride in tetrahydrofuran (4.16 ml, 8.32 mmol) and the mixture was heated at reflux for one hour. To the warm reaction mixture was added methyl 5-chloro-1-methyl-1H-pyrrolo[2,3-b]pyridine-2-carboxylate (0.89 g, 3.96 mmol) in tetrahydrofuran (10 ml) and the resulting mixture was heated overnight. Then the reaction was cooled to room temperature and the solvent was evaporated. The residue was taken up in ethyl acetate and washed four times with 0.5 N hydrochloric acid. The organic layer was washed with brine, dried (Na2SO4) and concentrated in vacuo. The residue was purified by column chromatography (silica gel; gradient of heptane to heptane/ethyl acetate 1/1) to give 5-chloro-N-(2-methoxy-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-1-methyl-1H-pyrrolo[2,3-b]pyridine-2-carboxamide (1.47 g).

Workup

  1. temperaturethe mixture was heated
  2. temperatureat reflux for one hour
  3. customTo the warm reaction mixture
  4. temperaturethe resulting mixture was heated overnight
  5. customthe solvent was evaporated
  6. washwashed four times with 0.5 N hydrochloric acid
  7. washThe organic layer was washed with brine
  8. dry with materialdried (Na2SO4)
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by column chromatography (silica gel; gradient of heptane to heptane/ethyl acetate 1/1)

Sources & evidence

ORD record
ord-d12add20efa84510ba6caae761c20a6b
Source dataset
uspto-grants-2014_02
Patent number
US08658794B2

Reaction notes

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