Reaktion #58698

Reaktionsgleichung

chloroacetonitrile

Acetonitrile

sodium bis(trimethylsilyl)amide

THF

Chloroacetonitrile

2-Chlorophenyl isothiocyanate

→

title compound

3-Amino-7-(2-chlorophenyl)-6-oxo-6,7-dihydrothieno[2,3-b]pyridine-2-carbonitrile

Lösungsmittel

EtOH

Reaktionsbedingungen

Aufarbeitung

1. 1
   Sonstigeto give a thick white precipitate
2. 2
   Sonstigeto give a brown solution
3. 3
   Temperaturthe mixture heated
4. 4
   Temperaturat reflux for 24 h
5. 5
   SonstigeVolatiles were removed in vacuo
6. 6
   workup.DISSOLUTIONthe residue dissolved in acetonitrile (100 mL)
7. 7
   Temperaturthe mixture heated at 50° C. for 1 h
8. 8
   workup.ADDITIONwas added
9. 9
   Temperaturheating
10. 10
    SonstigeSome of the acetonitrile (˜50 mL) was removed in vacuo and water
11. 11
    workup.ADDITIONwas added
12. 12
    Sonstigeto precipitate the product
13. 13
    FiltrationThe brown solid was filtered off
14. 14
    Waschenwashed with water (50 mL) and Et2O (50 mL)
15. 15
    Sonstigedried

Vorschrift

Acetonitrile (10 mL) was added to a solution of sodium bis(trimethylsilyl)amide (100 mL, 1.0M in THF, 100 mmol) in THF (50 mL) at −78° C. to give a thick white precipitate. 2-Chlorophenyl isothiocyanate (7.72 g, 45.45 mmol) was added to give a brown solution. The mixture was allowed to warm to r.t. over 1 h then diluted with EtOH (50 mL). N,N-Dimethyluracil (6.4 g, 45 mmol) was added and the mixture heated at reflux for 24 h. Volatiles were removed in vacuo and the residue dissolved in acetonitrile (100 mL). Chloroacetonitrile (2.85 mL, 45 mmol) was added and the mixture heated at 50° C. for 1 h, a second charge of chloroacetonitrile (2.85 mL, 45 mmol) was added and heating continued for 1.5 h. Some of the acetonitrile (˜50 mL) was removed in vacuo and water was added to precipitate the product. The brown solid was filtered off, washed with water (50 mL) and Et2O (50 mL) and dried to give the title compound as a brown solid (14.3 g, quant.). δH (DMSO-d6) 8.10 (1H, d, J 9.7 Hz), 7.75-7.73 (1H, m), 7.65-7.54 (3H, m), 7.14 (2H, br s, NH2), 6.54 (1H, d, J 9.7 Hz). LCMS (ES+) RT 2.97 minutes, 302 (M+H)+.

Quelle