2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 59409005, compound

HRID 1894737Notes

Reaction equation

HRID 1894737 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][CH:6]=[C:5]2[C:11]1[C:12](=[O:29])[NH:13][C:14](=[O:28])[C:15]=1[C:16]1[CH:17]=[C:18]2[C:23]3=[C:24]([CH2:26][CH2:27][N:22]3[CH2:21][CH2:20][CH2:19]2)[CH:25]=1.ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl.S([O-])([O-])=O.[Na+].[Na+]>O1CCCC1.O.C(OCC)(=O)C>[Br:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][CH:6]=[C:5]2[C:11]1[C:12](=[O:29])[NH:13][C:14](=[O:28])[C:15]=1[C:16]1[CH:17]=[C:18]2[C:23]3=[C:24]([CH:26]=[CH:27][N:22]3[CH2:21][CH2:20][CH2:19]2)[CH:25]=1

Participants

7

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 24437Sodium SulfiteHCID 59408993HCID 59408993, compound

Product 1

HCID 59409005HCID 59409005, compoundYield 85.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 3-(5-bromo-1H-indol-3-yl)-4-(1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-ij]quinolin-8-yl)-pyrrole-2,5-dione (300 mg, 0.668 mmol) in anhydrous tetrahydrofuran (15 ml) at room temperature was treated with 2,3-dichloro-5,6-dicyano-p-benzoquinone (182 mg, 0.802 mmol) and stirred for 30 minutes. The reaction was treated with 10% aqueous sodium sulfite (40 ml) and diluted with water (50 ml) and ethyl acetate (50 ml). The aqueous layer was removed and the organic layer was washed with saturated aqueous sodium bicarbonate (50 ml) then water (2×50 ml). The organic layer was dried over anhydrous sodium sulfate and evaporated to dryness. The residue was purified by flash column chromatography (SiO2, 1% methanol to 10% methanol in dichloromethane) to provide 3-(5-bromo-1H-indol-3-yl)-4-(5,6-dihydro-4H-pyrrolo[3,2,1-ij]quinolin-8-yl)-pyrrole-2,5-dione as an orange solid (255 mg). 400 MHz 1H NMR (DMSO-d6) δ: 11.94 (s, 1H), 10.95 (s, 1H), 7.99 (s, 1H), 7.45 (d, J=1.6 Hz, 1H), 7.33 (m, 2H), 7.08 (dd, J=6.8 and 1.6 Hz, 1H), 6.81 (d, J=1.6 Hz, 1H), 6.34 (d, J=2.8 Hz, 1H), 6.20 (d, J=2.0 Hz, 2H), 4.17 (m, 2H), 2.75 (m, 2H), 2.12 (m, 2H); LCMS: 446 and 448 [M+H].

Workup

  1. customThe aqueous layer was removed
  2. washthe organic layer was washed with saturated aqueous sodium bicarbonate (50 ml)
  3. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  4. customevaporated to dryness
  5. customThe residue was purified by flash column chromatography (SiO2, 1% methanol to 10% methanol in dichloromethane)

Sources & evidence

ORD record
ord-5524e26696ad4a508c871510d401e4e2
Source dataset
uspto-grants-2013_08
Patent number
US08513292B2

Reaction notes

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