Sodium borohydride → 3-Fluoro-4-(2-(4-(methylsulfonyl)phenyl)thieno[3,2-b]pyridin-7-yloxy)benzenamine

HRID 1261208Notes

Reaction equation

HRID 1261208 reaction equation
[F:1][C:2]1[CH:27]=[C:26]([N+:28]([O-])=O)[CH:25]=[CH:24][C:3]=1[O:4][C:5]1[CH:10]=[CH:9][N:8]=[C:7]2[CH:11]=[C:12]([C:14]3[CH:19]=[CH:18][C:17]([S:20]([CH3:23])(=[O:22])=[O:21])=[CH:16][CH:15]=3)[S:13][C:6]=12.[BH4-].[Na+]>C1COCC1.CO.Cl[Ni]Cl>[F:1][C:2]1[CH:27]=[C:26]([NH2:28])[CH:25]=[CH:24][C:3]=1[O:4][C:5]1[CH:10]=[CH:9][N:8]=[C:7]2[CH:11]=[C:12]([C:14]3[CH:15]=[CH:16][C:17]([S:20]([CH3:23])(=[O:21])=[O:22])=[CH:18][CH:19]=3)[S:13][C:6]=12

Participants

6

Reactant 2

HCID 4311764Sodium borohydrideHCID 587728787-(2-Fluoro-4-nitrophenoxy)-2-(4-(methylsulfonyl)phenyl)thieno[3,2-b]pyridine

Product 1

HCID 587728693-Fluoro-4-(2-(4-(methylsulfonyl)phenyl)thieno[3,2-b]pyridin-7-yloxy)benzenamineYield 51%

Reagents, catalysts & solvents 3

HCID 24385Nickel DichlorideCatalystHCID 887MethanolSolventHCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Nitro compound 48 (97 mg, 2 mmol) was dissolved in a mixture of THF (7 mL) and MeOH (15 mL); NiCl2×6H2O (130 mg, 0.5 mmol) was added and the solution was cooled to 0° C. To the cooled mixture NaBH4 (42 mg, 1.1 mmol) was added portion wise. The reaction was stirred for 20 min and quenched with 2 M HCl. The solvents were removed under reduced pressure and the residue was treated with concentrated ammonium hydroxide solution (pH 10) and extracted with EtOAc. The organic extract was dried over anhydrous sodium sulfate, filtered and evaporated. The residue was purified by column chromatography (eluent EtOAc) to afford the title compound 49 (46.7 mg, 51% yield) as a white solid 1H NMR (DMSO) δ (ppm): 8.52 (d, J=5.5 Hz, 1H), 8.25 (s, 1H), 8.15 (d, J=8.4 Hz, 2H), 8.03 (d, J=8.4 Hz, 2H), 7.63-7.58 (m, 2H), 7.56-7.52 (m, 2H), 7.13 (t, J=8.6 Hz, 1H), 6.61 (d, J=2.2 Hz, 1H), 6.56 (dd, J=10 Hz, 1H), 6.46 (dd, J=5.7 Hz, 1H), 5.57 (s, 2H), 3.29 (s, 3H), MS (m/z): 414.8 (M+H).

Workup

  1. customquenched with 2 M HCl
  2. customThe solvents were removed under reduced pressure
  3. additionthe residue was treated with concentrated ammonium hydroxide solution (pH 10)
  4. extractionextracted with EtOAc
  5. extractionThe organic extract
  6. dry with materialwas dried over anhydrous sodium sulfate
  7. filtrationfiltered
  8. customevaporated
  9. customThe residue was purified by column chromatography (eluent EtOAc)

Sources & evidence

ORD record
ord-c46572c3c25343b3b7fd389e0fb0f424
Source dataset
uspto-grants-2013_06
Patent number
US08470850B2

Reaction notes

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