Ethyl (2-oxo-cyclohex-3-enyl)acetate → Ethyl [4-(4-fluorophenyl)-2-oxo-cyclohexyl]acetate

HRID 12611

반응식

HRID 12611 반응식
[O:1]=[C:2]1[CH:7]=[CH:6][CH2:5][CH2:4][CH:3]1[CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10].[F:14][C:15]1[CH:20]=[CH:19][C:18]([Mg]Br)=[CH:17][CH:16]=1>CSC.O1CCCC1>[F:14][C:15]1[CH:20]=[CH:19][C:18]([CH:6]2[CH2:5][CH2:4][CH:3]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:2](=[O:1])[CH2:7]2)=[CH:17][CH:16]=1

참가 물질

5

반응물 2

HCID 13834278Ethyl (2-oxo-cyclohex-3-enyl)acetateHCID 178418676HCID 178418676, 화합물

생성물 1

HCID 91222586Ethyl [4-(4-fluorophenyl)-2-oxo-cyclohexyl]acetate

시약·촉매·용매 2

HCID 1068Dimethyl Sulfide용매HCID 8028Tetrahydrofuran용매

실험 절차

This ester (4 g, 0.022 mmol), copper (I) bromide-dimethyl sulfide complex (4.88 g, 0.023 mmol) in dimethyl sulfide (20 ml) and tetrahydrofuran (120 ml) was cooled to −40° C. under nitrogen and treated dropwise with 4-fluorophenylmagnesium bromide (1M solution in THF, 43.9 ml) so that the temperature did not rise above −40° C. Reaction was stirred for 20 minutes before quenching with 1N HCl (300 ml) and extracting the products with ether (3×300 ml). Combined organic phase washed with saturated sodium chloride, dried over magnesium sulfate and evaporated to dryness. The crude oil was purified by silica chromatography eluting with hexane-ethyl acetate mixtures (10-20%), to give ethyl [4-(4-fluorophenyl)-2-oxo-cyclohexyl]acetate as a colourless oil, 2.8 g. 1H NMR δ (ppm) (CDCl3): 7.26-7.11 (2H, m), 7.04-6.94 (2H, m), 4.18-4.11 (2H, m), 3.55-3.44 (1H, m), 3.00-2.90 (1H, m), 2.80-2.73 (2H, m), 2.69-2.55 (1H, m), 2.28-2.17 (2H, m), 2.10-1.88 (2H, m), 1.61-1.42 (1H, m) and 1.31-1.25 (3H, m).

후처리

  1. customdid not rise above −40° C
  2. customReaction
  3. custombefore quenching with 1N HCl (300 ml)
  4. extractionextracting the products with ether (3×300 ml)
  5. washCombined organic phase washed with saturated sodium chloride
  6. dry with materialdried over magnesium sulfate
  7. customevaporated to dryness
  8. customThe crude oil was purified by silica chromatography
  9. washeluting with hexane-ethyl acetate mixtures (10-20%)

출처 및 근거

ORD 기록
ord-2d4777b6081240f594287e9174a72b72
출처 데이터셋
uspto-grants-2010_06
특허 번호
US07728022B2

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