Epichlorohydrin → HCID 86609868, compound

HRID 746935Notes

Reaction equation

HRID 746935 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:12]3[CH2:13][N:14]([C:17](=[O:19])[CH3:18])[CH2:15][CH2:16][C:11]=3[NH:10][N:9]=2)=[CH:4][C:3]=1[N+:20]([O-:22])=[O:21].[C:23](=O)([O-])[O-].[Cs+].[Cs+].C([CH:31]1[O:33][CH2:32]1)Cl>CN(C=O)C.C(OCC)(=O)C.O>[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:12]3[CH:13]([CH3:23])[N:14]([C:17](=[O:19])[CH3:18])[CH2:15][CH2:16][C:11]=3[N:10]([CH:32]3[CH2:31][O:33]3)[N:9]=2)=[CH:4][C:3]=1[N+:20]([O-:22])=[O:21]

Participants

7

Reactant 3

HCID 7835EpichlorohydrinHCID 10796Cesium carbonateHCID 17975400HCID 17975400, compound

Product 1

HCID 86609868HCID 86609868, compoundYield 99.5%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

A solution of 1-[3-(4-chloro-3-nitro-phenyl)-1,4,6,7-tetrahydro-pyrazolo[4,3-c]pyridin-5-yl]-ethanone (6.4 g, 20.0 mmol) in DMF (60 mL) was treated with cesium carbonate (13.0 g, 40 mmol) and epichlorohydrin (15.6 mL, 200.0 mmol) at room temperature. The reaction mixture was stirred at room temperature for an additional 24 h before it was diluted with ethyl acetate (350 mL) and water (50 mL). The organic layer was separated, washed with water (2×50 mL), brine (50 mL), dried over sodium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (silica, 10% acetone/CH2Cl2) to provide 7.5 g (83%) of a light yellow powder. MS (electrospray): m/z 377.0 (377.0, calculated for C17H17ClN4O4, [M+H]+). 1H NMR (CDCl3, 400 MHz, a mixture of two rotamers): 8.15-8.05 (m, 1H), 7.75-7.65 (m, 1H), 7.55-7.45 (m, 1H), 4.80-4.65 (m, 1.2H), 4.60 (s, 0.8H), 4.45-4.35 (m, 1H), 4.08-4.02 (m, 1H), 3.92-3.80 (m, 1H), 3.70-3.63 (m, 1H), 3.30-3.20 (m, 1H), 2.90-2.67 (m, 3H), 2.55-2.48 (m, 1H), 2.15 (s, 1.7H), 2.10 (s, 1.3H).

Workup

  1. customThe organic layer was separated
  2. washwashed with water (2×50 mL), brine (50 mL)
  3. dry with materialdried over sodium sulfate
  4. concentrationconcentrated under reduced pressure
  5. customThe residue was purified by column chromatography (silica, 10% acetone/CH2Cl2)

Sources & evidence

ORD record
ord-cb43b50a2f2347b2bf0d507041cd2f47
Source dataset
uspto-grants-2008_07
Patent number
US07393850B2

Reaction notes

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