(4-Fluorophenyl)dimethylphosphine oxide → 1-(Dimethyl-phosphinoyl)-4-nitro-benzene

HRID 719242Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 719242
[CH3:1][P:2]([CH3:11])([C:4]1[CH:9]=[CH:8][C:7](F)=[CH:6][CH:5]=1)=[O:3].[Li][N+:13]([O-:15])=[O:14]>CN1C(=O)N(C)CCC1.[Cl-].[Na+].O.CC(O)C>[CH3:1][P:2]([CH3:11])([C:4]1[CH:9]=[CH:8][C:7]([N+:13]([O-:15])=[O:14])=[CH:6][CH:5]=1)=[O:3]

Komponenten

6

Edukt 2

HCID 21897903(4-Fluorophenyl)dimethylphosphine oxideHCID 178506934HCID 178506934, Verbindung

Produkt 1

HCID 218979121-(Dimethyl-phosphinoyl)-4-nitro-benzeneAusbeute 45,1 %

Reagenzien, Katalysatoren, Lösungsmittel 3

HCID 3776IsopropanolLösungsmittelHCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-LösungsmittelHCID 57417360Sodium chloride; waterLösungsmittel

Versuchsvorschrift

A sealed pressure flask, flushed with N2, containing a mixture of 3.90 g (22.7 mmol) of 1-(Dimethyl-phosphinoyl)-4-fluoro-benzene and 6.0 g (113.3 mmol) of LiNO2 (for prep see, W. C. Ball and H. H. Abram J. Chem. Soc. 1913, 103, 2130–2134) in 27 mL of DMPU (1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone) was stirred at ambient temperature for 5–10 min (to dissolve fluoro compound) then heated at 190° C. for 3 days. The resulting dark brown solution was cooled to ambient temperature, diluted with 300 mL of brine, then extracted with EtOAc (10×100 mL) until the aqueous layer showed little or no evidence of product by HPLC. The combined organics were dried over MgSO4 and concentrated. The excess DMPU was removed via short-path distillation (120° C./0.3 mm) to provide a semi-solid, which was dissolved in a minimum amount of iPrOH and purified by silica gel flash chromatography (eluted with 5% iPrOH/DCM, then 10% iPrOH/DCM, then 15% iPrOH/DCM) to provide 2.04 g of an yellow solid: 1H NMR (300 MHz, DMSO-d6) δ 8.34 (dd, J=8.7, 1.9 Hz, 2H), 8.07 (dd, J=10.6, 8.8 Hz, 2H), 1.75 (s, 3H), 1.70 (s, 3H). 31P NMR (121 MHz, DMSO-d6) δ 37.89.

Aufarbeitung

  1. customA sealed pressure flask, flushed with N2
  2. additioncontaining
  3. temperaturethen heated at 190° C. for 3 days
  4. temperatureThe resulting dark brown solution was cooled to ambient temperature
  5. extractionextracted with EtOAc (10×100 mL) until the aqueous layer
  6. dry with materialThe combined organics were dried over MgSO4
  7. concentrationconcentrated
  8. customThe excess DMPU was removed via short-path distillation (120° C./0.3 mm)
  9. customto provide a semi-solid, which
  10. custompurified by silica gel flash chromatography (
  11. washeluted with 5% iPrOH/DCM

Quellen und Nachweise

ORD-Eintrag
ord-f4d9bf4e227b475fab613b0a22bdf83a
Quelldatensatz
uspto-grants-2006_11
Patentnummer
US07132427B2

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