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

HRID 12611

反応式

HRID 12611 の反応式
[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

参加物

5

反応物 2

HCID 13834278Ethyl (2-oxo-cyclohex-3-enyl)acetateHCID 178418676HCID 178418676、化合物

生成物 1

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

試薬・触媒・溶媒 2

HCID 1068Dimethyl Sulfide溶媒HCID 8028Tetrahydrofuran溶媒

実験手順

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).

後処理

  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%)

出典と根拠

ORDレコード
ord-2d4777b6081240f594287e9174a72b72
出典データセット
uspto-grants-2010_06
特許番号
US07728022B2

関連ノート

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