4-Nitro-1-(oxan-2-yl)-1H-pyrazole-3-carbaldehyde → HCID 178480424, compound

HRID 2274425Notes

Reaction equation

HRID 2274425 reaction equation
[N+:1]([C:4]1[C:5]([CH:15]=O)=[N:6][N:7]([CH:9]2[CH2:14][CH2:13][CH2:12][CH2:11][O:10]2)[CH:8]=1)([O-:3])=[O:2].[F:17][C:18]1[CH:19]=[C:20]([NH2:33])[C:21]([NH2:32])=[CH:22][C:23]=1[N:24]1[CH2:30][CH2:29][CH2:28][N:27]([CH3:31])[CH2:26][CH2:25]1>CN(C=O)C>[F:17][C:18]1[C:23]([N:24]2[CH2:30][CH2:29][CH2:28][N:27]([CH3:31])[CH2:26][CH2:25]2)=[CH:22][C:21]2[NH:32][C:15]([C:5]3[C:4]([N+:1]([O-:3])=[O:2])=[CH:8][N:7]([CH:9]4[CH2:14][CH2:13][CH2:12][CH2:11][O:10]4)[N:6]=3)=[N:33][C:20]=2[CH:19]=1

Participants

4

Reactant 2

HCID 224778374-Nitro-1-(oxan-2-yl)-1H-pyrazole-3-carbaldehydeHCID 57812833HCID 57812833, compound

Product 1

HCID 178480424HCID 178480424, compoundYield 33.9%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
22 °C

Procedure

18 g of 4-nitro-1-(tetrahydropyran-2-yl)-1H-pyrazole-3-carbaldehyde and 664 mg of ferric chloride are added to a solution of 19.1 g of 4-fluoro-5-(4-methylperhydro-1,4-diazepin-1-yl)benzene-1,2-diamine in 406 mL of DMF. The reaction medium is stirred at 22° C. for 4 hours. After evaporation, the reaction crude is purified on a column 8 cm in diameter, with 3 kg of silica having a porosity of 0.063-0.2 mm. The elution is carried out with 2 L of pure dichloromethane and then 4 L of dichloromethane containing 10% of methanol, and then with dichloromethane containing 15% of methanol. 12 g of 5-fluoro-6-(4-methylperhydro-1,4-diazepin-1-yl)-2-[4-nitro-1-(tetrahydropyran-2-yl)-1H-pyrazol-3-yl]-1H-benzimidazole are isolated. 1H NMR (400 MHz, DMSO-d6, δ in ppm): 1.41 to 2.31 (m, 8H); 2.91 (s, 3H); from 3.22 to 3.67 (m, 8H); 3.72 (m, 1H); 3.99 (m, 1H); 5.69 (dd, J=2.5 and 9.5 Hz, 1H); 7.32 (d, J=8.0 Hz, 1H); 7.75 (d, J=12.0 Hz, 1H); 9.40 (s, 1H). EI mass spectrum: m/z=443: M+. —m/z=373: (M−C4H8N)+—m/z=289: (m/z=373—C5H8O)+—m/z=84: C5H8O+. (base peak)—m/z=57: C3H7N+.

Workup

  1. customAfter evaporation
  2. customthe reaction crude
  3. customis purified on a column 8 cm in diameter, with 3 kg of silica having a porosity of 0.063-0.2 mm
  4. washThe elution

Sources & evidence

ORD record
ord-971754706d45439d85eed01af23de636
Source dataset
uspto-grants-2015_09
Patent number
US09126969B2

Reaction notes

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