Hydrochloric Acid → Dimethyl-(3-(trifluoromethyl)-phenyl)-malonate

HRID 341124

반응식

HRID 341124 반응식
C(=O)([O-])[O-].[Cs+].[Cs+].[C:7]([O:14][CH3:15])(=[O:13])[CH2:8][C:9]([O:11][CH3:12])=[O:10].I[C:17]1[CH:22]=[CH:21][CH:20]=[C:19]([C:23]([F:26])([F:25])[F:24])[CH:18]=1.Cl>>[F:24][C:23]([F:26])([F:25])[C:19]1[CH:18]=[C:17]([CH:8]([C:7]([O:14][CH3:15])=[O:13])[C:9]([O:11][CH3:12])=[O:10])[CH:22]=[CH:21][CH:20]=1

참가 물질

5

반응물 4

HCID 313Hydrochloric AcidHCID 7943Dimethyl malonateHCID 10796Cesium carbonateHCID 67868Benzene, 1-iodo-3-(trifluoromethyl)-

생성물 1

HCID 57348216Dimethyl-(3-(trifluoromethyl)-phenyl)-malonate수율 58%

실험 절차

Dioxane (100 mL) was purged with nitrogen gas for 10 minutes. Phenanthrolene (1.0 g) and copper (I) iodide (1.0 g) were added to the dioxane, the suspension was allowed to stir under a nitrogen atmosphere for 5 minutes, and then cesium carbonate (18.72 g, 57.45 mmol), dimethyl malonate (5.46 g, 50.6 mmol), and 1-iodo-3-(trifluoromethyl)benzene (12.5 g, 46.0 mmol) were added. The reaction mixture was heated to reflux for 18 hours and then cooled to room temperature. Aqueous 1N HCl was added to the reaction mixture, the layers were separated, and the aqueous layer was extracted with ethyl acetate (3×100 mL). The combined organic layers were dried over magnesium sulfate and filtered. Celite® diatomaceous filter aid (5 g) was added to the filtrate, and the resulting suspension was concentrated under reduced pressure at 50° C. to yield a solid consisting of the crude product adsorbed onto Celite®. This solid was purified by silica gel chromatography eluting with a gradient of 100% hexanes to 25% ethyl acetate in hexanes to yield 7.36 g (58.0%) of the title product. 1H NMR (CDCl3) δ 7.59-7.65 (m, 3H), 7.49 (t, 1H), 4.70 (s, 1H), 3.76 (s, 6H).

후처리

  1. customDioxane (100 mL) was purged with nitrogen gas for 10 minutes
  2. additionPhenanthrolene (1.0 g) and copper (I) iodide (1.0 g) were added to the dioxane
  3. temperatureThe reaction mixture was heated
  4. temperatureto reflux for 18 hours
  5. customthe layers were separated
  6. extractionthe aqueous layer was extracted with ethyl acetate (3×100 mL)
  7. dry with materialThe combined organic layers were dried over magnesium sulfate
  8. filtrationfiltered
  9. additionCelite® diatomaceous filter aid (5 g) was added to the filtrate
  10. concentrationthe resulting suspension was concentrated under reduced pressure at 50° C.
  11. customto yield a solid
  12. customThis solid was purified by silica gel chromatography
  13. washeluting with a gradient of 100% hexanes to 25% ethyl acetate in hexanes

출처 및 근거

ORD 기록
ord-a6790f4b6b75457f872779f2d8c9a24e
출처 데이터셋
uspto-grants-2014_11
특허 번호
US08895738B2

연결된 노트

불러오는 중…