Water → HCID 67773630, compound

HRID 1963078Notes

Reaction equation

HRID 1963078 reaction equation
[CH2:1]([O:3][C:4]([C:6]1[NH:7][CH:8]=[C:9]([CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[C:20]([F:24])[C:19]=2[CH3:25])[C:10]=1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=[O:5])[CH3:2].[H-].[Na+].O.CC(=O)OCC.C[N:36](C=O)C>>[CH2:1]([O:3][C:4]([C:6]1[N:7]([NH2:36])[CH:8]=[C:9]([CH2:17][C:18]2[CH:23]=[CH:22][CH:21]=[C:20]([F:24])[C:19]=2[CH3:25])[C:10]=1[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1)=[O:5])[CH3:2]

Participants

6

Reactant 5

HCID 962WaterHCID 6228DimethylformamideHCID 8857Ethyl AcetateHCID 24758Sodium hydrideHCID 67774815HCID 67774815, compound

Product 1

HCID 67773630HCID 67773630, compound

Conditions

Temperature
0 °C

Procedure

To a solution of the compound of step 4 (6.748 g, 20.00 mmol) in 60 ml of anhydrous DMF under a nitrogen atmosphere at 0° C. was added sodium hydride (60% in mineral oil, 0.960 g, 24 mmol) in small portions. After stirring for 10 min at 0° C., the mixture was allowed to warm to room temperature over 15 min. After cooling to 0° C. again, 0-(2,4-dinitro-phenyl)-hydroxylamine (cf. C. Legault et al., J. Org. Chem. 68 (2003), 7119; P. H. Boyle et al., ARKIVOC (2003) (vii), 67; 4.779 g, 24.00 mmol) was added in small portions and the mixture was stirred at room temperature for 1 h. Water (250 ml) and EA (250 ml) were added and the organic phase was washed twice with 125 ml each of a 1 N sodium hydroxide solution and 125 ml of brine, dried over magnesium sulfate, filtered and evaporated to dryness under reduced pressure. The residue was purified by chromatography on silica gel, first eluting with cyclohexane/DCM (40:60, then 20:80, then 0:100), then with DCM/EA (97.5:2.5, then 95:5) to give 6.33 g of the title compound as a beige solid melting at 87-88° C.

Workup

  1. temperatureto warm to room temperature over 15 min
  2. temperatureAfter cooling to 0° C. again
  3. stirringthe mixture was stirred at room temperature for 1 h
  4. washthe organic phase was washed twice with 125 ml each of a 1 N sodium hydroxide solution and 125 ml of brine
  5. dry with materialdried over magnesium sulfate
  6. filtrationfiltered
  7. customevaporated to dryness under reduced pressure
  8. customThe residue was purified by chromatography on silica gel
  9. washfirst eluting with cyclohexane/DCM (40:60

Sources & evidence

ORD record
ord-cfc3b75f0f0343d6a475062c6c630ced
Source dataset
uspto-grants-2013_04
Patent number
US08415336B2

Reaction notes

Loading…