반응 #11413

ord-eae56509a51f4eea830b1991cad1252d

반응 조건

상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    온도whilst maintaining the temperature below 20° C
  2. 2
    온도was then heated
  3. 3
    온도to reflux
  4. 4
    workup.STIRRINGstirred at this temperature for 3 hours
  5. 5
    온도to cool to ambient temperature
  6. 6
    기타The two phase system was separated
  7. 7
    추출the aqueous layer was extracted with ethyl acetate (5×100 mL)
  8. 8
    세척washed with water (2×100 mL)
  9. 9
    건조dried over Na2SO4
  10. 10
    농축concentrated under reduced pressure
  11. 11
    기타to give an orange oily solid
  12. 12
    workup.WAITafter standing at ambient temperature for 1 hour
  13. 13
    여과the precipitate was filtered off
  14. 14
    기타re-crystallized from ethyl acetate/hexane

실험 절차

To a stirred solution of ethyl 2-chlorophenoxyacetate (32.0 g, 149 mmol) in dichloromethane (75 mL) at ambient temperature under nitrogen was added succinic anhydride (22.4 g, 224 mmol). The reaction mixture was cooled in ice-water and to this was added portion wise aluminum trichloride (59.6 g, 447 mmol), whilst maintaining the temperature below 20° C. The reaction mixture was then allowed to stir at ambient temperature for 20 minutes and was then heated to reflux and stirred at this temperature for 3 hours. The reaction mixture was allowed to cool to ambient temperature, then poured into a mixture of ice, water (200 ml) and HCl (10 N, 100 ml). The two phase system was separated and the aqueous layer was extracted with ethyl acetate (5×100 mL). All organic layers were then combined and washed with water (2×100 mL), dried over Na2SO4, and concentrated under reduced pressure to give an orange oily solid. Hexane (300 mL) was added, and after standing at ambient temperature for 1 hour, the precipitate was filtered off and re-crystallized from ethyl acetate/hexane to give 9 as a light yellow powder (21.5 g, 46% yield, 98% pure by LCMS and 1H NMR), 1H NMR (400 MHz; CDCl3): δ 7.79 (m, 1H); 7.66 (m, 1H); 6.79 (m, 1H); 4.90 (s, 2H); 4.12 (q, 2H); 2.82 (m, 2H); 2.42 (m, 2H); 1.30 (t, 3H).

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US07098211B2uspto-grants-2006_08