Reaktion #438846

Reaktionsgleichung

5-tert-butyl-2-methoxy-1,3-dinitrobenzene

sodium sulfide nonahydrate

→

title compound

Ausbeute 30.0%

5-tert-Butyl-2-methoxy-3-nitroaniline

Ausbeute 30.0%

Lösungsmittel

EtOAc

EtOAc

water

—

hexanes

Reaktionsbedingungen

Aufarbeitung

1. 1
   workup.ADDITIONAliquate® 336 (0.8 g, 5 mole %) was added in a single portion
2. 2
   workup.DISSOLUTIONAll solids dissolved
3. 3
   FiltrationThe mixture was filtered
4. 4
   Temperaturwarm through a pad of diatomaceous earth
5. 5
   Sonstigeto remove insolubles
6. 6
   Waschenthe filter cake was washed with fresh EtOAc
7. 7
   SonstigeThe clarified two-phase mixture was separated
8. 8
   Waschenthe organic layer was washed with sodium carbonate solution
9. 9
   TrocknenAfter drying over magnesium sulfate
10. 10
    Einengenthe solution was concentrated under reduced pressure to a thick, dark oil
11. 11
    ExtraktionThis oil was extracted three times with refluxing hexanes
12. 12
    Sonstigeleaving behind a dark residue
13. 13
    ExtraktionThe orange extract
14. 14
    Sonstigefrom which the warm supernatant was decanted
15. 15
    TemperaturThe resulting orange solution was heated back
16. 16
    Temperaturto reflux
17. 17
    workup.ADDITIONtreated with both activated charcoal and diatomaceous earth
18. 18
    FiltrationThe solution was filtered hot
19. 19
    Waschenthe filter cake washed with hot hexanes
20. 20
    SonstigeRe-heating the orange filtrate resulted in a clear solution
21. 21
    TemperaturQuickly cooling the solution in an ice/acetone bath
22. 22
    Sonstigeresulted in the deposition of an orange/yellow precipitate
23. 23
    Temperaturto cool for 1 h
24. 24
    Filtrationfiltered
25. 25
    WaschenThe filter cake was washed with a small portion of cold hexanes
26. 26
    Sonstigedried on the filter

Vorschrift

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). Aliquate® 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%).

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