Stannous chloride dihydrate → HCID 22285321, compound

HRID 1061783Notes

Reaction equation

HRID 1061783 reaction equation
[F:1][C:2]1[CH:3]=[C:4]([C:11]2[C:12]([C:17]#[N:18])=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH:5]=[C:6]([N+:8]([O-])=O)[CH:7]=1.O.O.[Sn](Cl)Cl>C(O)C.O1CCCC1>[NH2:8][C:6]1[CH:7]=[C:2]([F:1])[CH:3]=[C:4]([C:11]2[C:12]([C:17]#[N:18])=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH:5]=1

Participants

5

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 22285268HCID 22285268, compound

Product 1

HCID 22285321HCID 22285321, compoundYield 58%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A cooled (0° C.) suspension of 3′-fluoro-5′-nitrobiphenyl-2-carbonitrile (8.9 g, 37 mmol) in ethanol (70 mL) and tetrahydrofuran (70 mL) was treated with tin(II) chloride dihydrate (29 g, 129 mmol) and the mixture was stirred at ambient temperature for 4 h. The solvent was removed in vacuo and the residue treated with ice-cold 2 N sodium hydroxide (400 mL). The resulting slurry was stirred for 30 min then extracted with dichloromethane (2×400 mL). The organics were combined, washed with water and brine, dried over anhydrous magnesium sulfate, filtered and pre-adsorbed onto silica. Purification by dry flash chromatography on silica, eluting with dichloromethane containing 0.5% triethylamine, afforded 5′-amino-3′-fluorobiphenyl-2-carbonitrile as a white solid (4.5 g, 58%): δH (400 MHz, CDCl3) 3.90 (2H, br), 6.45 (1H, ddd, J 8, 2 and 2), 6.58-6.63 (2H, m), 7.44 (1H, ddd, J 8, 8 and 2), 7.48 (1H, dd, J 8 and 2), 7.62 (1H, ddd, J 8, 8 and 2), 7.74 (1H, dd, J 8 and 2).

Workup

  1. temperatureA cooled
  2. customThe solvent was removed in vacuo
  3. additionthe residue treated with ice-cold 2 N sodium hydroxide (400 mL)
  4. stirringThe resulting slurry was stirred for 30 min
  5. extractionthen extracted with dichloromethane (2×400 mL)
  6. washwashed with water and brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered and pre-adsorbed onto silica
  9. customPurification
  10. customby dry flash chromatography on silica
  11. washeluting with dichloromethane containing 0.5% triethylamine

Sources & evidence

ORD record
ord-40936104e87543f2a1860f00132858fa
Source dataset
uspto-grants-2005_11
Patent number
US06960598B2

Reaction notes

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