Sodium Sulfide → 4-[2-(3-Aminophenyl)pyrazolo[1,5-a]pyridin-3-yl]-N-phenyl-2-pyrimidinamine

HRID 1157542Notes

Reaction equation

HRID 1157542 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C:10]2[C:18]([C:19]3[CH:24]=[CH:23][N:22]=[C:21]([NH:25][C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)[N:20]=3)=[C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][N:12]3[N:11]=2)[CH:7]=[CH:8][CH:9]=1)([O-])=O.[S-2].[Na+].[Na+]>O1CCOCC1.O>[NH2:1][C:4]1[CH:5]=[C:6]([C:10]2[C:18]([C:19]3[CH:24]=[CH:23][N:22]=[C:21]([NH:25][C:26]4[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=4)[N:20]=3)=[C:13]3[CH:14]=[CH:15][CH:16]=[CH:17][N:12]3[N:11]=2)[CH:7]=[CH:8][CH:9]=1

Participants

5

Reactant 2

HCID 14804Sodium SulfideHCID 577372514-[2-(3-Nitrophenyl)pyrazolo[1,5-a]pyridin-3-yl]-N-phenyl-2-pyrimidinamine

Product 1

HCID 577372234-[2-(3-Aminophenyl)pyrazolo[1,5-a]pyridin-3-yl]-N-phenyl-2-pyrimidinamineYield 62%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

To a solution of 4-[2-(3-nitrophenyl)pyrazolo[1,5-a]pyridin-3-yl]-N-phenyl-2-pyrimidinamine (809 mg, 1.98 mmol) in 1,4-dioxane (16 mL) was added sodium sulfide nonhydrate (1.05 g, 6 mmol) in water (4 mL). The mixture was heated at 90° C. for 5 h, allowed to cool to rt and concentrated in vacuo. The residue was diluted with EtOAc and water. The organic layer was separated and the aqueous layer is extracted with EtOAc. The combined organic layers were dried over MgSO4, filtered and concentrated to give a dark solid. The crude material was purified by silica gel chromatography (hexanes/EtOAc 30-50%) to afford the titled product (462 mg, 62% yield). 1H NMR (400 MHz, CDCl3): δ 3.75 (brs, 2H), 6.63 (d, 1H, J=5.3 Hz), 6.78 (m, 1H), 6.91 (m, 1H), 6.96-7.00 (m, 2H), 7.06 (m, 1H), 7.16 (m, 1H), 7.22-7.36 (m, 4H), 7.65 (m, 1H), 8.17 (d, 1H, J=5.3 Hz), 8.42 (m, 1H), 8.52 (m, 1H); ES-LC/MS m/z=379 [M+H]+.

Workup

  1. temperatureto cool to rt
  2. concentrationconcentrated in vacuo
  3. additionThe residue was diluted with EtOAc and water
  4. customThe organic layer was separated
  5. extractionthe aqueous layer is extracted with EtOAc
  6. dry with materialThe combined organic layers were dried over MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customto give a dark solid
  10. customThe crude material was purified by silica gel chromatography (hexanes/EtOAc 30-50%)

Sources & evidence

ORD record
ord-6c3b8b4578d54be1830ff4c74c30ddad
Source dataset
uspto-grants-2010_10
Patent number
US07807673B2

Reaction notes

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