Hydrochloric Acid → (4-Aminophenyl)(4-fluorophenyl)methanone

HRID 383733Notes

Reaction equation

HRID 383733 reaction equation
O.O.[Sn](Cl)Cl.Cl.[F:7][C:8]1[CH:24]=[CH:23][C:11]([C:12]([C:14]2[CH:19]=[CH:18][C:17]([N+:20]([O-])=O)=[CH:16][CH:15]=2)=[O:13])=[CH:10][CH:9]=1>COCCOC.CCO>[NH2:20][C:17]1[CH:18]=[CH:19][C:14]([C:12](=[O:13])[C:11]2[CH:23]=[CH:24][C:8]([F:7])=[CH:9][CH:10]=2)=[CH:15][CH:16]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 61436Stannous chloride dihydrateHCID 97658Methanone, (4-fluorophenyl)(4-nitrophenyl)-

Product 1

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

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 80711,2-DimethoxyethaneSolvent

Procedure

A solution of tin (II) chloride dihydrate (1.05 g, 4.7 mmol) in cone 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 5 h 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 5 h 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-02f3431cf6ee4d449791eb58ce772219
Source dataset
uspto-grants-2013_02
Patent number
US08367667B2

Reaction notes

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