반응 #58698

반응 방정식

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

용매

EtOH

반응 조건

후처리

1. 1
   기타to give a thick white precipitate
2. 2
   기타to give a brown solution
3. 3
   온도the mixture heated
4. 4
   온도at reflux for 24 h
5. 5
   기타Volatiles were removed in vacuo
6. 6
   workup.DISSOLUTIONthe residue dissolved in acetonitrile (100 mL)
7. 7
   온도the mixture heated at 50° C. for 1 h
8. 8
   workup.ADDITIONwas added
9. 9
   온도heating
10. 10
    기타Some of the acetonitrile (˜50 mL) was removed in vacuo and water
11. 11
    workup.ADDITIONwas added
12. 12
    기타to precipitate the product
13. 13
    여과The brown solid was filtered off
14. 14
    세척washed with water (50 mL) and Et2O (50 mL)
15. 15
    기타dried

실험 절차

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)+.

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