Reaktion #70669

Reaktionsgleichung

4,8-dihydrobenzo[1,2-b:4,5-b′]dithiophen-4,8-dione

m-tolylmagnesium bromide

hydrochloric acid

tin (II) chloride

m-tolylmagnesium bromide

→

4,8-di-m-tolylbenzo[1,2-b:4,5-b′]dithiophene

Lösungsmittel

tetrahydrofuran

Reaktionsbedingungen

Aufarbeitung

1. 1
   SonstigeA clean and dry 2000 ml round bottom flask
2. 2
   Sonstigeequipped
3. 3
   Temperaturwith reflux condenser, magnetic stir bar
4. 4
   Sonstigethermometer with adapter was prepared
5. 5
   Sonstigepurged
6. 6
   TemperaturHeat
7. 7
   workup.DISSOLUTIONto dissolve this material
8. 8
   SonstigeThe reaction vessel was placed into a water bath
9. 9
   workup.ADDITIONaddition
10. 10
    Sonstigethe vessel was removed from the water bath
11. 11
    Temperaturheated
12. 12
    Temperaturto reflux for 1 hour
13. 13
    SonstigeThe reaction was then removed
14. 14
    Temperaturfrom heat
15. 15
    Temperaturthe reaction was again heated
16. 16
    Temperaturto reflux for 1 hour
17. 17
    SonstigeThe reaction was subsequently removed
18. 18
    Temperaturfrom heat
19. 19
    Temperaturcool to room temperature overnight
20. 20
    workup.ADDITIONadded to the reaction via syringe
21. 21
    TemperaturThe reaction vessel was again heated
22. 22
    Temperaturto reflux for 1 hour
23. 23
    Sonstigeremoved
24. 24
    Temperaturfrom heat
25. 25
    Temperaturto cool to room temperature
26. 26
    SonstigeSolvent was removed by rotary evaporation
27. 27
    workup.DISSOLUTIONthe crude mixture was nearly dissolved
28. 28
    WaschenThe volume was washed once with DI H2O (500 mL)
29. 29
    workup.ADDITIONthe organic layer containing solids
30. 30
    Sonstigewas collected
31. 31
    SonstigeSolids were removed by vacuum filtration
32. 32
    Sonstigecollected
33. 33
    Waschenwashed in hot methanol
34. 34
    TrocknenThe filtrate was dried over anhydrous magnesium sulfate
35. 35
    Filtrationfiltered
36. 36
    Sonstigeremoved of solvent by rotary evaporation
37. 37
    workup.ADDITIONTo the remaining crude material acetone (25.0 ml) and methanol (500.0 ml) were added
38. 38
    Temperaturheated
39. 39
    Temperaturto reflux in trituration for 1 hour
40. 40
    FiltrationThe resulting solids in solution were vacuum-filtered
41. 41
    Sonstigecollected
42. 42
    SonstigeAll solids collected during purification

Vorschrift

A clean and dry 2000 ml round bottom flask equipped with reflux condenser, magnetic stir bar, and thermometer with adapter was prepared, purged, and then charged with 4,8-dihydrobenzo[1,2-b:4,5-b′]dithiophen-4,8-dione (7.34 g, 0.0333 mol). Anhydrous tetrahydrofuran (900.0 ml) was then added to this flask by cannula and stirring was initiated. Heat was applied to the reaction vessel to dissolve this material. The reaction vessel was placed into a water bath and m-tolylmagnesium bromide solution (100 ml, 0.1000 mol) was added via cannula. Following addition, the vessel was removed from the water bath and heated to reflux for 1 hour. The reaction was then removed from heat and allowed to cool to room temperature. m-tolylmagnesium bromide solution (100 ml, 0.1000 mol) was added via cannula and the reaction was again heated to reflux for 1 hour. The progress of the reaction was monitored by GC-MS and no starting material was present. The reaction was subsequently removed from heat and cool to room temperature overnight. A hydrochloric acid (160.0 ml, 10%)/tin (II) chloride (30.05 g, 0.1333 mol) solution was then prepared and added to the reaction via syringe. The reaction vessel was again heated to reflux for 1 hour, then removed from heat and allowed to cool to room temperature. Solvent was removed by rotary evaporation. Ethyl acetate (500.0 ml) was and the crude mixture was nearly dissolved. The volume was washed once with DI H2O (500 mL), and the organic layer containing solids was collected. Solids were removed by vacuum filtration, collected, and washed in hot methanol. The filtrate was dried over anhydrous magnesium sulfate, filtered, and removed of solvent by rotary evaporation. To the remaining crude material acetone (25.0 ml) and methanol (500.0 ml) were added and heated to reflux in trituration for 1 hour. The resulting solids in solution were vacuum-filtered and collected. All solids collected during purification were proved to be pure by NMR spectroscopy.

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