反应 #2329962

ord-2a1630fbe7284a9a981742b333d01e9e

溶剂

反应条件

详细条件
See reaction.notes.procedure_details.

后处理

  1. 1
    其他(ca. 2 min)
  2. 2
    workup.STIRRINGThe reaction mixture is stirred overnight (˜16 h) at room temperature
  3. 3
    萃取the mixture is extracted with ethyl acetate (3×70 ml)
  4. 4
    干燥The extracts are dried (Na2SO4)
  5. 5
    其他evaporated under reduced pressure
  6. 6
    其他The residue is purified by column chromatography on silica
  7. 7
    洗涤eluting with petrol/ethyl acetate (10:0 to 4:1)

实验过程

To a mixture of zinc powder (1.80 g, 27.5 mmol) in anhydrous DMA (20 ml) is added iodine (0.5 g, 1.97 mmol). This mixture is stirred until the red color of iodine disappeared (ca. 2 min), followed by the addition of 3-(6-bromohexyloxymethyl)-3-ethyloxetane (5.0 g, 17.9 mmol) and the resultant mixture is stirred at 85° C. for 4.5 h, then cooled to room temperature. In another flask charged with anhydrous THF (30 ml) is added 1-bromo-4-iodobenzene (7.0 g, 24.74 mmol) and Pd(dppf)Cl2 (0.5 g, 0.61 mmol). This mixture is stirred for 10 min, then the organic zinc reagent above is introduced. The reaction mixture is stirred overnight (˜16 h) at room temperature. Sat. aq. NH4Cl solution is added and the mixture is extracted with ethyl acetate (3×70 ml). The extracts are dried (Na2SO4) and evaporated under reduced pressure. The residue is purified by column chromatography on silica, eluting with petrol/ethyl acetate (10:0 to 4:1), to give a brown oil (2.6 g, 41%). 1H NMR (300 MHz, CDCl3): δ(ppm) 7.35 (d, J=8.4 Hz, 2H, Ar—H), 7.01 (d, J=8.4 Hz, 2H, Ar—H), 4.43 (d, J=5.7 Hz, 2H, OCH2), 4.34 (d, J=5.7 Hz, 2H, OCH2), 3.48 (s, 2H, OCH2), 3.41 (t, J=6.4 Hz, 2H, OCH2), 2.53 (t, J=7.9 Hz, 2H, ArCH2), 1.72 (q, J=7.6 Hz, 2H, CH2), 1.56 (m, 4H, CH2), 1.34 (m, 4H, CH2); 0.86 (t, J=7.6 Hz 3H, CH3); 13C NMR (75 MHz, CDCl3): δ (ppm) 141.6 (quat.), 131.2 (CH), 130.2 (CH), 119.3 (quat.), 78.4 (OCH2), 73.4 (OCH2), 71.4 (OCH2), 43.4 (quat.), 35.3 (CH2), 31.3 (CH2), 29.5 (CH2), 29.0 (CH2), 26.8 (CH2), 26.0 (CH2), 8.2 (CH3).

来源

DOI: 10.6084/m9.figshare.5104873.v1专利: US07674397B2uspto-grants-2010_03