Sodium hydride → [2-[3,5-bis(Acetoxymethyl)pyrazol-1-yl]-5-nitrophenyl]phenyl methanone

HRID 236730Notes

Reaction equation

HRID 236730 reaction equation
[C:1]([O:4][CH2:5][C:6]1[CH:10]=[C:9]([CH2:11][O:12][C:13](=[O:15])[CH3:14])[NH:8][N:7]=1)(=[O:3])[CH3:2].[H-].[Na+].F[C:19]1[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][C:20]=1[C:21]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)=[O:22]>CN(C=O)C>[C:13]([O:12][CH2:11][C:9]1[CH:10]=[C:6]([CH2:5][O:4][C:1](=[O:3])[CH3:2])[N:7]([C:19]2[CH:32]=[CH:31][C:30]([N+:33]([O-:35])=[O:34])=[CH:29][C:20]=2[C:21]([C:23]2[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=2)=[O:22])[N:8]=1)(=[O:15])[CH3:14]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 123775343,5-DiacetoxymethylpyrazoleHCID 12377535(2-Fluoro-5-nitrophenyl)(phenyl)methanone

Product 1

HCID 12377536[2-[3,5-bis(Acetoxymethyl)pyrazol-1-yl]-5-nitrophenyl]phenyl methanone

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

A solution of 4.2 g. (20 mmol) of 3,5-diacetoxymethylpyrazole in 15 ml. of DMF was added dropwise to a suspension of 960 mg. (20 mmol) of NaH (50% in mineral oil) in 25 ml. of DMF stirred at 0° and under argon. After the evolution of H2 had ceased, 4.9 g. (20 mmol) of 2-fluoro-5-nitrobenzophenone was added in one portion. After stirring at 0° for 4 hours, the mixture was poured into ice-water and extracted with EtOAc. The organic phase was washed with dil. brine, dried (MgSO4) and concentrated. The residue was chromatographed on silica gel using benzene/EtOAc (1:1) as eluent. Removal of the solvents gave crude end product as a gum which was not purified further. The nmr (CDCl3) had signals at: δ2.00 (3H, s, CH3), 2.07 (3H, s, CH3), 4.82 (2H, s, CH2), 5.10 (2 H, s, CH2) 6.33 (1H, s, C=CH), and 7.30-8.67 (8H, m, C6H5 +C6H3).

Workup

  1. extractionextracted with EtOAc
  2. washThe organic phase was washed with dil. brine
  3. dry with materialdried (MgSO4)
  4. concentrationconcentrated
  5. customThe residue was chromatographed on silica gel
  6. customRemoval of the solvents
  7. customgave crude end product as a gum which
  8. customwas not purified further

Sources & evidence

ORD record
ord-3e9751721a454d938ad3f5ecde4d7f3c
Source dataset
uspto-grants-1979_06
Patent number
US04157331

Reaction notes

Loading…