Pyridine → HCID 86651943, compound

HRID 1615209Notes

Reaction equation

HRID 1615209 reaction equation
[N:1]1[CH:6]=[CH:5][C:4](/[CH:7]=[CH:8]/[C:9]2[C:17]3[C:12](=[CH:13][C:14]([C:18]#N)=[CH:15][CH:16]=3)[NH:11][N:10]=2)=[CH:3][CH:2]=1.[PH2]([O-])=[O:21].[Na+].N1C=CC=CC=1>CC(O)=O.N1C=CC=CC=1.O.[Ni]>[N:1]1[CH:6]=[CH:5][C:4](/[CH:7]=[CH:8]/[C:9]2[C:17]3[C:12](=[CH:13][C:14]([CH:18]=[O:21])=[CH:15][CH:16]=3)[NH:11][N:10]=2)=[CH:3][CH:2]=1

Participants

7

Reactant 3

HCID 1049PyridineHCID 66734432(E)-3-(2-(pyridin-4-yl)vinyl)-1H-indazole-6-carbonitrileHCID 178527019HCID 178527019, compound

Product 1

HCID 86651943HCID 86651943, compoundYield 30.1%

Reagents, catalysts & solvents 3

HCID 935NickelCatalystHCID 962WaterSolvent3×HCID 165292Pyridinium acetateSolvent

Conditions

Temperature
55 °C

Procedure

To a solution of (E)-3-(2-(pyridin-4-yl)vinyl)-1H-indazole-6-carbonitrile (246 mg, 1 mmol) in HOAc/pyridine (3 mL/6 mL) was added a solution of sodium hypophosphite (352 mg, 4 mmol) in H2O (3 mL), followed by Raney-Nickel 2400 (slurry in H2O, 0.2 mL). The resulting mixture was heated at 55° C. (oil temp.) for 1 h then cooled to rt. Water (30 mL) was added and the mixture was extracted with EtOAc (30 mL×3). The combined extracts were washed with H2O (20 mL×3), brine (10 mL) and dried (Na2SO4). Removal of solvent gave a yellow solution containing pyridine. H2O (60 mL) was added with swirling and large amounts of yellow precipitate formed which was collected by suction filtration and rinsed with H2O. After dying under high vacuum, the title compound (75 mg, 30%) was obtained as a beige solid. 1H NMR (400 MHz, DMSO-d6) δ 13.90 (s, 1H, NH), 10.14 (s, 1H, CHO), 8.57 (d, J=5.6 Hz, 2H), 8.40 (d, J=8.4 Hz, 1H), 8.20 (s, 1H), 7.89 (d, J=16.8 Hz, 1H), 7.73-7.69 (m, 3H), 7.55 (d, J=16.4 Hz, 1H). MS ESI 247.0 [M+H]+, calcd for [C15H11N3O+H]+ 247.1.

Workup

  1. temperaturethen cooled to rt
  2. extractionthe mixture was extracted with EtOAc (30 mL×3)
  3. washThe combined extracts were washed with H2O (20 mL×3), brine (10 mL)
  4. dry with materialdried (Na2SO4)
  5. customRemoval of solvent
  6. customgave a yellow solution
  7. customlarge amounts of yellow precipitate formed which
  8. filtrationwas collected by suction filtration
  9. washrinsed with H2O

Sources & evidence

ORD record
ord-88dcf3905d9e4835b3b4783da1f1238e
Source dataset
uspto-grants-2014_07
Patent number
US08765748B2

Reaction notes

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