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

HRID 1743367노트

반응식

HRID 1743367 반응식
[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]

참가 물질

6

반응물 2

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

생성물 1

HCID 218979121-(Dimethyl-phosphinoyl)-4-nitro-benzene수율 45.1%

시약·촉매·용매 3

HCID 3776Isopropanol용매HCID 816462(1H)-Pyrimidinone, tetrahydro-1,3-dimethyl-용매HCID 57417360Sodium chloride; water용매

실험 절차

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.

후처리

  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

출처 및 근거

ORD 기록
ord-83ba64357a4e4d4ab8e389bc70a72a71
출처 데이터셋
uspto-grants-2006_03
특허 번호
US07009054B2

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