1-Iodo-4-nitrobenzene → p-Allylnitrobenzene

HRID 269982

반응식

HRID 269982 반응식
[CH2:1]([Sn](CCCC)(CCCC)CCCC)[CH:2]=[CH2:3].I[C:18]1[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][CH:19]=1.[F-].[K+]>O1CCOCC1.C(OCC)C.[Pd].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Cu]I>[CH2:3]([C:18]1[CH:23]=[CH:22][C:21]([N+:24]([O-:26])=[O:25])=[CH:20][CH:19]=1)[CH:2]=[CH2:1]

참가 물질

8

반응물 3

HCID 124951-Iodo-4-nitrobenzeneHCID 90628AllyltributylstannaneHCID 522689Potassium Fluoride

생성물 1

HCID 595953p-Allylnitrobenzene수율 55%

시약·촉매·용매 4

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)촉매HCID 11979704Tetrakis(triphenylphosphine)palladium촉매HCID 3283Diethyl Ether용매HCID 312751,4-Dioxane용매

실험 절차

Add allyl tri-n-butylstannane (30.10 mmol, 9.33 ml) dropwise to a stirred solution of 4-iodo-nitrobenzene (5 g, 20.07 mmol), tetrakis-(triphenylphosphine) palladium(0) (1.16 g, 1 mmol) and copper (I) iodide (306 mg, 1.6 mmol) in 50 ml of dry 1,4-dioxane under argon atmosphere. Reflux the mixture for 24 hours and then cool to room temperature. Dilute the solution with 40 ml of diethyl ether and add 20 ml of saturated solution of KF and stir for 2 hours. Filter the mixture and wash the organic layer with water (20 ml), brine (20 ml) and dry over sodium sulfate. Evaporate the solution under reduced pressure and purify the residue by flash chromatography on silica gel using hexane-ethyl acetate as eluent (20:1) to afford 1.80 g (55%) of 1-allyl-4-nitrobenzene. Add a solution of 3-chloro-peroxybenzoic acid (5.98 g, 24.28 mmol), in 20 ml of dichloromethane to a solution of 1-allyl-4-nitro-benzene (1.8 g, 11.04 mmol) in 50 ml of dichloromethane and stir the mixture at room temperature overnight. Quench with saturated NaHCO3 (15 ml), and wash the organic layer three times with saturated NaHCO3 and dry over magnesium sulfate. Evaporate under reduced pressure to afford 1.4 g (71%) of the title compound.

후처리

  1. temperatureReflux the mixture for 24 hours
  2. filtrationFilter the mixture
  3. washwash the organic layer with water (20 ml), brine (20 ml)
  4. dry with materialdry over sodium sulfate
  5. customEvaporate the solution under reduced pressure
  6. custompurify the residue by flash chromatography on silica gel

출처 및 근거

ORD 기록
ord-eb64e9e5d5d0411b9bee90b4279b0e0e
출처 데이터셋
uspto-grants-2008_11
특허 번호
US07449477B2

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