Sodium sulfide nonahydrate → 5-(tert-Butyl)-2-methoxy-3-nitroaniline

HRID 1884597Notes

Reaction equation

HRID 1884597 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([N+:16]([O-])=O)[C:8]([O:14][CH3:15])=[C:9]([N+:11]([O-:13])=[O:12])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].O.O.O.O.O.O.O.O.O.[S-2].[Na+].[Na+]>CCOC(C)=O.O.CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)C.[Cl-]>[C:1]([C:5]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[C:8]([O:14][CH3:15])=[C:7]([CH:6]=1)[NH2:16])([CH3:4])([CH3:2])[CH3:3]

Participants

6

Reactant 2

HCID 73972Sodium sulfide nonahydrateHCID 42526024-tert-Butyl-2,6-dinitroanisole

Product 1

HCID 112068635-(tert-Butyl)-2-methoxy-3-nitroanilineYield 30%

Reagents, catalysts & solvents 3

HCID 21218Trioctylmethylammonium chlorideCatalystHCID 962WaterSolventHCID 8857Ethyl AcetateSolvent2×

Procedure

To a suspension of 5-tert-butyl-2-methoxy-1,3-dinitrobenzene (10.2 g, 0.04 mol) in EtOAc (150 mL) was added in a single portion a solution of sodium sulfide nonahydrate (19.2 g, 0.08 mol) in water (200 mL). Aliquat® 336 (0.8 g, 5 mole %) was added in a single portion, and the two-phase mixture was brought to a reflux. All solids dissolved, and the mixture became red/brown. After about 3 h, TLC (3:1 hexanes:EtOAc) revealed almost complete loss of starting material. The mixture was filtered warm through a pad of diatomaceous earth to remove insolubles, and the filter cake was washed with fresh EtOAc. The clarified two-phase mixture was separated, and the organic layer was washed with sodium carbonate solution, followed by water and then saturated sodium chloride solution. After drying over magnesium sulfate, the solution was concentrated under reduced pressure to a thick, dark oil. This oil was extracted three times with refluxing hexanes, leaving behind a dark residue. The orange extract deposited some more dark oil, from which the warm supernatant was decanted. The resulting orange solution was heated back to reflux, and treated with both activated charcoal and diatomaceous earth. The solution was filtered hot, and the filter cake washed with hot hexanes. Re-heating the orange filtrate resulted in a clear solution. Quickly cooling the solution in an ice/acetone bath and scratching the flask with a glass rod resulted in the deposition of an orange/yellow precipitate. The suspension was allowed to cool for 1 h, and then filtered. The filter cake was washed with a small portion of cold hexanes, and then dried on the filter, providing the title compound as a yellow/orange powder (2.6 g, 30%).

Workup

  1. dissolutionAll solids dissolved
  2. filtrationThe mixture was filtered
  3. temperaturewarm through a pad of diatomaceous earth
  4. customto remove insolubles
  5. washthe filter cake was washed with fresh EtOAc
  6. customThe clarified two-phase mixture was separated
  7. washthe organic layer was washed with sodium carbonate solution
  8. dry with materialAfter drying over magnesium sulfate
  9. concentrationthe solution was concentrated under reduced pressure to a thick, dark oil
  10. extractionThis oil was extracted three times with refluxing hexanes
  11. customleaving behind a dark residue
  12. extractionThe orange extract
  13. customfrom which the warm supernatant was decanted
  14. temperatureThe resulting orange solution was heated back
  15. temperatureto reflux
  16. additiontreated with both activated charcoal and diatomaceous earth
  17. filtrationThe solution was filtered hot
  18. washthe filter cake washed with hot hexanes
  19. customRe-heating the orange filtrate resulted in a clear solution
  20. temperatureQuickly cooling the solution in an ice/acetone bath
  21. customresulted in the deposition of an orange/yellow precipitate
  22. temperatureto cool for 1 h
  23. filtrationfiltered
  24. washThe filter cake was washed with a small portion of cold hexanes
  25. customdried on the filter

Sources & evidence

ORD record
ord-9522e70b12274771904357e3f5468573
Source dataset
uspto-grants-2004_07
Patent number
US06765009B2

Reaction notes

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