Stannous chloride dihydrate → 5'-Amino-2'-fluorobiphenyl-2-carbonitrile

HRID 2183863Notes

Reaction equation

HRID 2183863 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-])=O)=[CH:4][C:3]=1[C:11]1[C:12]([C:17]#[N:18])=[CH:13][CH:14]=[CH:15][CH:16]=1.O.O.[Sn](Cl)Cl>C(O)C.O1CCCC1>[NH2:8][C:5]1[CH:6]=[CH:7][C:2]([F:1])=[C:3]([C:11]2[C:12]([C:17]#[N:18])=[CH:13][CH:14]=[CH:15][CH:16]=2)[CH:4]=1

Participants

5

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 114478612'-Fluoro-5'-nitrobiphenyl-2-carbonitrile

Product 1

HCID 114699075'-Amino-2'-fluorobiphenyl-2-carbonitrileYield 75.4%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 8028TetrahydrofuranSolvent

Procedure

A cooled (0° C.) suspension of 2′-fluoro-5′-nitrobiphenyl-2-carbonitrile (24.2 g, 100 mmol) in ethanol (150 ml) and tetrahydrofuran (150 ml) was treated with tin(II) chloride dihydrate (67.7 g, 300 mmol) and the mixture was stirred to ambient temperature over 12 h. The solvent was removed in vacuo and the residue treated with ice-cold 2N sodium hydroxide (750 ml). The resulting slurry was stirred for 60 min then extracted with dichloromethane (2×400 ml). The organics were combined, washed with water, brine, dried over anhydrous magnesium sulfate, filtered and concentrated to give a red solid. Crystallisation from toluene gave 5′-amino-2′-fluorobiphenyl-2-carbonitrile as a cream-coloured solid (16 g, 75%): δH (400 MHz, CDCl3) 3.65 (2H, br), 6.67-6.73 (2H, m), 7.00 (1H, t, J 9), 7.44-7.49 (2H, m), 7.64 (1H, td, J 9 and 2), 7.75 (1H, dd, J 8 and 2); m/z (ES+) 213 (M++H).

Workup

  1. temperatureA cooled
  2. customThe solvent was removed in vacuo
  3. additionthe residue treated with ice-cold 2N sodium hydroxide (750 ml)
  4. stirringThe resulting slurry was stirred for 60 min
  5. extractionthen extracted with dichloromethane (2×400 ml)
  6. washwashed with water, brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customto give a red solid
  11. customCrystallisation from toluene

Sources & evidence

ORD record
ord-2b750229908743a29e9d9eef607a8293
Source dataset
uspto-grants-2005_05
Patent number
US06900215B2

Reaction notes

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