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

HRID 48928

反応式

HRID 48928 の反応式
[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]

参加物

6

反応物 2

HCID 21897903(4-Fluorophenyl)dimethylphosphine oxideHCID 178506934HCID 178506934、化合物

生成物 1

HCID 218979121-(Dimethyl-phosphinoyl)-4-nitro-benzene収率 45.1%

試薬・触媒・溶媒 3

HCID 3776Isopropanol溶媒HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-溶媒HCID 57417360Sodium chloride; water溶媒

実験手順

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.

後処理

  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

出典と根拠

ORDレコード
ord-e5c0c3d34b494d6a94dacbfd45c76ba6
出典データセット
uspto-grants-2004_03
特許番号
US06706699B2

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