2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 69935267, compound

HRID 341108Notes

Reaction equation

HRID 341108 reaction equation
[F:1][C:2]1[CH:30]=[CH:29][C:5]([CH2:6][N:7]2[C:16]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=3[C:10]3=[N:17][N:18]([C:21]4[CH:28]=[CH:27][CH:26]=[CH:25][C:22]=4[CH:23]=[O:24])[C:19](=[O:20])[C:9]3=[CH:8]2)=[CH:4][CH:3]=1.[BH4-].[Na+].ClC1C(=O)C(C#N)=C(C#N)C(=O)C=1Cl>ClCCl>[F:1][C:2]1[CH:3]=[CH:4][C:5]([CH2:6][N:7]2[C:16]3[CH:15]=[CH:14][CH:13]=[CH:12][C:11]=3[C:10]3=[N:17][N:18]([C:21]4[CH:28]=[CH:27][CH:26]=[CH:25][C:22]=4[CH2:23][OH:24])[C:19](=[O:20])[C:9]3=[CH:8]2)=[CH:29][CH:30]=1

Participants

5

Reactant 3

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 4311764Sodium borohydrideHCID 86668690HCID 86668690, compound

Product 1

HCID 69935267HCID 69935267, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2-[5-(4-Fluorobenzyl)-3-oxo-3,5-dihydro-2H-pyrazolo[4,3-c]quinolin-2-yl]benzaldehyde (Example 786) (60 mg, 0.15 mmol) was dissolved in dichloromethane (3 mL), treated with sodium borohydride (7.4 mg, 0.20 mmol, 1.3 equiv) and stirred at ambient temperature for 24 hours. The mixture was washed with brine (5 mL), dried with sodium sulfate, filtered, and concentrated in vacuo. The residue was dissolved in dichloromethane (3 mL), treated with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (56 mg, 0.25 mmol, 1.6 equiv) and stirred at ambient temperature for 3 hours. The mixture was concentrated in vacuo and the residue was purified by preparative reverse phase HPLC (eluting 80:20 to 5:95; water containing 0.1% trifluoroacetic acid:acetonitrile containing 0.1% trifluoroacetic acid), providing the title compound: 1H-NMR (400 MHz, CD3OD) δ 9.12 (1H, s), 8.19 (1H, d, J=7.9 Hz), 7.75 (1H, d, J=8.6 Hz), 7.66-7.60 (2H, m), 7.55-7.51 (1H, m), 7.44-7.38 (5H, m), 7.20 (2H, d, J=8.8 Hz), 5.73 (2H, s), 4.45 (2H, s), ppm; low resolution mass spectrometry (ES+) m/z 399.9 [(M+H)+; calculated for C24H18FN3O2: 400.1].

Workup

  1. washThe mixture was washed with brine (5 mL)
  2. dry with materialdried with sodium sulfate
  3. filtrationfiltered
  4. concentrationconcentrated in vacuo
  5. dissolutionThe residue was dissolved in dichloromethane (3 mL)
  6. stirringstirred at ambient temperature for 3 hours
  7. concentrationThe mixture was concentrated in vacuo
  8. customthe residue was purified by preparative reverse phase HPLC (eluting 80:20 to 5:95; water containing 0.1% trifluoroacetic acid:acetonitrile containing 0.1% trifluoroacetic acid)

Sources & evidence

ORD record
ord-505660a0862b412b894a0c95710d8ecb
Source dataset
uspto-grants-2014_11
Patent number
US08895580B2

Reaction notes

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