Stannous chloride dihydrate → (4-Aminophenyl)(4-fluorophenyl)methanone

HRID 912564Notes

Reaction equation

HRID 912564 reaction equation
O.O.[Sn](Cl)Cl.[F:6][C:7]1[CH:23]=[CH:22][C:10]([C:11]([C:13]2[CH:18]=[CH:17][C:16]([N+:19]([O-])=O)=[CH:15][CH:14]=2)=[O:12])=[CH:9][CH:8]=1>Cl.COCCOC.CCO>[NH2:19][C:16]1[CH:17]=[CH:18][C:13]([C:11](=[O:12])[C:10]2[CH:22]=[CH:23][C:7]([F:6])=[CH:8][CH:9]=2)=[CH:14][CH:15]=1

Participants

6

Reactant 2

HCID 61436Stannous chloride dihydrateHCID 97658Methanone, (4-fluorophenyl)(4-nitrophenyl)-

Product 1

HCID 577826(4-Aminophenyl)(4-fluorophenyl)methanoneYield 83.6%

Reagents, catalysts & solvents 3

HCID 313Hydrochloric AcidSolventHCID 702EthanolSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

A solution of tin (II) chloride dihydrate (1.05 g, 4.7 mmol) in conc hydrochloric acid (4.2 mL) was added to 4-fluoro-4′-nitrobenzophenone (0.37 g, 1.5 mmol) in a mixture of DME (4 mL) and EtOH (5 mL) at such a rate that the internal temperature remained under 35° C. After 5h the reaction mixture was quenched by addition to ice-water (40 mL). The mixture was diluted with DCM (25 mL), made basic (pH=11) by addition of 10% NaOH, and then extracted with DCM (2×25 mL). The combined extracts were washed with water and brine, dried (anhyd Na2SO4) and concentrated under reduced pressure. The crude material was chromatographed (silica, EtOAc/Hex, 0:100 to 40:60) to afford 4′-amino-4-fluorobenzophenone (0.27 g, 83%) as a white solid. 1H-NMR (DMSO-d6) δ 7.68 (2H, dd, J=5.6, 8.8), 7.51 (2H, d, J=8.8), 7.32 (2H, app t, J=8.8), 6.61 (2H, d, J=8.8), 6.18 (2H, br s). A solution of tin (II) chloride dihydrate (1.05 g, 4.7 mmol) in conc hydrochloric acid (4.2 mL) was added to 4-fluoro-4′-nitrobenzophenone (0.37 g, 1.5 mmol) in a mixture of DME (4

Workup

  1. customremained under 35° C
  2. customAfter 5h the reaction mixture was quenched by addition to ice-water (40 mL)
  3. additionThe mixture was diluted with DCM (25 mL)
  4. additionby addition of 10% NaOH
  5. extractionextracted with DCM (2×25 mL)
  6. washThe combined extracts were washed with water and brine
  7. dry with materialdried (anhyd Na2SO4)
  8. concentrationconcentrated under reduced pressure
  9. customThe crude material was chromatographed (silica, EtOAc/Hex, 0:100 to 40:60)

Sources & evidence

ORD record
ord-35d0e244360940da8ac5b698f94a4519
Source dataset
uspto-grants-2011_09
Patent number
US08026237B2

Reaction notes

Loading…