2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 58093335, compound

HRID 474986Notes

Reaction equation

HRID 474986 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:13]3[CH2:12][CH2:11][CH2:10][CH2:9][C:8]=3[NH:7][C:6]=2[N:14]=1.ClC1C(=O)C(C#N)=C(C#N)C(=[O:23])C=1Cl>C1COCC1.O.C([O-])(O)=O.[Na+]>[Br:1][C:2]1[CH:3]=[CH:4][C:5]2[C:13]3[C:12](=[O:23])[CH2:11][CH2:10][CH2:9][C:8]=3[NH:7][C:6]=2[N:14]=1

Participants

6

Reactant 2

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 58093412HCID 58093412, compound

Product 1

HCID 58093335HCID 58093335, compoundYield 39.2%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 516892Sodium BicarbonateSolvent

Procedure

A solution of 2-bromo-6,7,8,9-tetrahydro-5H-pyrido[2,3-b]indole (3.84 g, 15.2 mmol) in THF (135 mL) and H2O (15.2 mL) was cooled to 0° C. and treated with a solution of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (6.92 g, 30.5 mmol) in THF (60.3 mL) at such a rate that the reaction mixture did not exceed 0° C. The resulting solution was warmed to ambient temperature and stirred for 5 h. The solution was diluted with saturated NaHCO3 solution (100 mL), and the aqueous solution was extracted with EtOAc (3×75 mL). The combined organic extracts were dried over Na2SO4, filtered and concentrated to dryness under reduced pressure. Flash chromatography (80 g ISCO dry load 80:18:2 CH2Cl2/MeOH/NH4OH, 1000 mL) followed by trituration with MeOH provided the title compound (1.58 g, 39%) as an off-white solid: 1H NMR (500 MHz, THF-d8) δ 8.23 (d, J=8.0 Hz, 1H), 7.32 (d, J=8.0, 1H), 4.73 (s, 1H), 3.02 (t, J=8.0 Hz, 2H), 2.51-2.47 (m, 2H), 2.27-2.22 (m, 2H); ESI MS m/z 265 [M+H]+.

Workup

  1. customdid not exceed 0° C
  2. extractionthe aqueous solution was extracted with EtOAc (3×75 mL)
  3. dry with materialThe combined organic extracts were dried over Na2SO4
  4. filtrationfiltered
  5. concentrationconcentrated to dryness under reduced pressure
  6. dry with materialFlash chromatography (80 g ISCO dry load 80:18:2 CH2Cl2/MeOH/NH4OH, 1000 mL)

Sources & evidence

ORD record
ord-61e97b9057324802be32d323e4a0dd3e
Source dataset
uspto-grants-2014_01
Patent number
US08637501B2

Reaction notes

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