2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → 1H-Pyrrolo[2,3-B]pyridine, 5-bromo-1-[(1,1-dimethylethyl)dimethylsilyl]-

HRID 1515599Notes

Reaction equation

HRID 1515599 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[CH2:10][CH2:9][N:8]([Si:11]([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:13])[CH3:12])[C:5]2=[N:6][CH:7]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>ClCCl.C(=O)(O)[O-].[Na+]>[Br:1][C:2]1[CH:3]=[C:4]2[CH:10]=[CH:9][N:8]([Si:11]([C:14]([CH3:17])([CH3:16])[CH3:15])([CH3:12])[CH3:13])[C:5]2=[N:6][CH:7]=1

Participants

5

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 587309295-Bromo-1-(tert-butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine

Product 1

HCID 497590181H-Pyrrolo[2,3-B]pyridine, 5-bromo-1-[(1,1-dimethylethyl)dimethylsilyl]-Yield 97.6%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 516892Sodium BicarbonateSolvent

Procedure

To a stirred solution of 5-bromo-1-(tert-butyl-dimethyl-silanyl)-2,3-dihydro-1H-pyrrolo[2,3-b]pyridine (17.0 g, 54.3 mmol) in dichloromethane (700 mL) was added 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (12.3 g, 54.3 mmol) in one portion. After 1 h, the resulting black mixture was diluted with a saturated aqueous sodium bicarbonate solution and stirred vigorously for 30 min. The solids were filtered off and the filtrate was separated. The aqueous layer was extracted with ethyl acetate. The combined organic solutions were dried over anhydrous sodium sulfate, concentrated in vacuo to afford 5-bromo-1-(tert-butyl-dimethyl-silanyl)-1H-pyrrolo[2,3-b]pyridine (16.5 g, 97%) which was used in the next step without further purification: 1H NMR (400 MHz, CDCl3) δ ppm 0.64 (s, 6H), 0.94 (s, 9H), 6.49 (d, J=3.4 Hz, 1H), 7.27 (d, J=3.4 Hz, 1H), 8.00 (d, J=2.3 Hz, 1H), 8.31 (d, J=2.3 Hz, 1H).

Workup

  1. filtrationThe solids were filtered off
  2. customthe filtrate was separated
  3. extractionThe aqueous layer was extracted with ethyl acetate
  4. dry with materialThe combined organic solutions were dried over anhydrous sodium sulfate
  5. concentrationconcentrated in vacuo

Sources & evidence

ORD record
ord-bfcab5cb4c2f4dac8e0754b57374b24e
Source dataset
uspto-grants-2012_07
Patent number
US08222416B2

Reaction notes

Loading…