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

HRID 1994201Notes

Reaction equation

HRID 1994201 reaction equation
C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N.[Br:15][C:16]1[CH:17]=[C:18]2[CH2:24][CH2:23][N:22]([Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:27])[CH3:26])[C:19]2=[N:20][CH:21]=1.C([O-])(O)=O.[Na+]>C(Cl)Cl.P([O-])([O-])([O-])=O>[Br:15][C:16]1[CH:17]=[C:18]2[CH:24]=[CH:23][N:22]([Si:25]([C:28]([CH3:31])([CH3:30])[CH3:29])([CH3:26])[CH3:27])[C:19]2=[N:20][CH:21]=1

Participants

6

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 516892Sodium BicarbonateHCID 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%

Reagents, catalysts & solvents 2

HCID 1061PhosphateSolventHCID 6344DichloromethaneSolvent

Procedure

DDQ (about 380 mg, 1.68 mmol) was added in portions to a solution of 4 (525 mg, 1.68 mmol) in a mixture of CH2Cl2 (90 mL) and 0.2 M phosphate buffer pH 7 solution (910 μL) until full consumption of the starting material (TLC). Then, saturated aqueous NaHCO3 solution (22 mL) was added, and the reaction mixture stirred for 0.5 h. The organic layer was separated and the aqueous layer was extracted with CH2Cl2 (3×20 mL). The combined organic solutions were dried (MgSO4), concentrated and purified by SGC with hexane:CH2Cl2 as eluent (in gradient up to 20% CH2Cl2) to give 26 (505 mg, 97%) as a clear oil; 1H NMR (400 MHz, CDCl3) δ 0.62 (s, 6H), 0.93 (s, 9H), 6.47 (d, J=3.5 Hz, 1H), 7.24 (d, J=3.5 Hz, 1H), 7.97 (d, J=2.2 Hz, 1H), 8.28 (d, J=2.2 Hz, 1H).

Workup

  1. customThe organic layer was separated
  2. extractionthe aqueous layer was extracted with CH2Cl2 (3×20 mL)
  3. dry with materialThe combined organic solutions were dried (MgSO4)
  4. concentrationconcentrated
  5. custompurified by SGC with hexane

Sources & evidence

ORD record
ord-e4986ef3576e46e4a90abb01c8fd9c3b
Source dataset
uspto-grants-2010_01
Patent number
US07652137B2

Reaction notes

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