Epichlorohydrin → HCID 17975402, compound

HRID 970104Notes

Reaction equation

HRID 970104 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(=O)([O-])[O-].[Cs+].[Cs+].[CH2:29]([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[CH2:13][N:14]([C:17](=[O:19])[CH3:18])[CH2:15][CH2:16][C:11]=3[N:10]([CH2:29][CH:31]3[CH2:32][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 17975402HCID 17975402, 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-e6c270ece8dc45d9ba1178f2a0a2a210
Source dataset
uspto-grants-2007_12
Patent number
US07309703B2

Reaction notes

Loading…