Sodium hydride → Di-tert-butyl 2-(4-methyl-2-nitrophenyl)malonate

HRID 1968953Notes

Reaction equation

HRID 1968953 reaction equation
[C:1]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])(=[O:10])[CH2:2][C:3]([O:5][C:6]([CH3:9])([CH3:8])[CH3:7])=[O:4].[H-].[Na+].F[C:19]1[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][C:20]=1[N+:26]([O-:28])=[O:27]>CN(C)C=O.O>[CH3:25][C:22]1[CH:23]=[CH:24][C:19]([CH:2]([C:3]([O:5][C:6]([CH3:7])([CH3:8])[CH3:9])=[O:4])[C:1]([O:11][C:12]([CH3:15])([CH3:14])[CH3:13])=[O:10])=[C:20]([N+:26]([O-:28])=[O:27])[CH:21]=1

Participants

6

Reactant 3

HCID 24758Sodium hydrideHCID 68324Di-tert-butyl malonateHCID 1362874-Fluoro-3-nitrotoluene

Product 1

HCID 57856684Di-tert-butyl 2-(4-methyl-2-nitrophenyl)malonateYield 29.1%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Conditions

Temperature
0 °C

Procedure

A stirred solution of di-tert-butyl malonate (1.5 mL, 6.70 mmol) in N, N-dimethylformamide (15 mL) at 0° C. under argon was treated portionwise over 10 minutes with sodium hydride (276 mg of 60% oil dispersion, 6.90 mmol) and stirred at 0° C. for 15 minutes before allowing to warm to room temperature over 1 hour. A white precipitate was produced. The stirred mixture was cooled to 0° C. and treated with a solution of 4-fluoro-3-nitrotoluene (1.0 g, 6.45 mmol) in N,N-dimethylformamide (2 mL) and a deep purple colour was immediately formed. This mixture was stirred at room temperature for 28 hours then heated at 70° C. for 6 hours. The mixture was cooled, then diluted with water (100 mL) and extracted with Et2O (2×50 mL). The combined extract was washed with water (70 mL), dried (Na2SO4) and concentrated under vacuum. The residue was purified by chromatography on silica gel (40 g) eluting with toluene to afford the title compound as a yellow oil (660 mg, 29%).

Workup

  1. temperatureto warm to room temperature over 1 hour
  2. customA white precipitate was produced
  3. temperatureThe stirred mixture was cooled to 0° C.
  4. customa deep purple colour was immediately formed
  5. stirringThis mixture was stirred at room temperature for 28 hours
  6. temperaturethen heated at 70° C. for 6 hours
  7. temperatureThe mixture was cooled
  8. extractionextracted with Et2O (2×50 mL)
  9. extractionThe combined extract
  10. washwas washed with water (70 mL)
  11. dry with materialdried (Na2SO4)
  12. concentrationconcentrated under vacuum
  13. customThe residue was purified by chromatography on silica gel (40 g)
  14. washeluting with toluene

Sources & evidence

ORD record
ord-2a660bbef6df410280773e3017029c19
Source dataset
uspto-grants-2013_04
Patent number
US08426443B2

Reaction notes

Loading…