Diethyl Ether → Ethyl 2,2-dimethyl-4-oxocyclohexane-1-carboxylate

HRID 2202734ノート

反応式

HRID 2202734 の反応式
C[Li].[CH3:3]COCC.[CH3:8][C:9]1[CH:10]([C:16]([O:18][CH2:19][CH3:20])=[O:17])[CH2:11][CH2:12][C:13](=[O:15])[CH:14]=1.[Cl-].[NH4+]>[Cu]I.CCOC(C)=O>[CH3:8][C:9]1([CH3:3])[CH2:14][C:13](=[O:15])[CH2:12][CH2:11][CH:10]1[C:16]([O:18][CH2:19][CH3:20])=[O:17]

参加物

7

反応物 4

HCID 3283Diethyl Ether2 回HCID 25517Ammonium ChlorideHCID 790204-Carbethoxy-3-methyl-2-cyclohexen-1-oneHCID 178418348HCID 178418348、化合物

生成物 1

HCID 118343006Ethyl 2,2-dimethyl-4-oxocyclohexane-1-carboxylate収率 68%

試薬・触媒・溶媒 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)触媒HCID 8857Ethyl Acetate溶媒

反応条件

温度
-40 °C

実験手順

Methyllithium (170 mL of a 1.6 M solution with Et2O, 260 mmol) was added to a stirring mixture of copper (I) iodide (25 g, 130 mmol) and Et2O (130 mL), at −40° C. under a nitrogen atmosphere. After stirring for 10 min at −40° C., ethyl 2-methyl-4-oxo-2-cyclohexene-1-carboxylate (12 g, 66 mmol) was added. After stirring for 30 min at −40° C., the reaction mixture was allowed to warm to −20° C. After stirring for 90 min at −20° C., saturated aqueous ammonium chloride and EtOAc were added sequentially, the mixture was partitioned between more saturated aqueous ammonium chloride and EtOAc, the layers were separated, the organic material washed sequentially with saturated aqueous ammonium chloride (2×) and brine, dried (Na2SO4), filtered, and the filtrate was concentrated. The residue was dissolved with DCM, silica gel (39 g) was added to the solution, and the volatiles were removed under reduced pressure. The residue was subjected to flash chromatography on silica gel (gradient elution; 19:1 to 9:1 hexane-EtOAc) to give ethyl 2,2-dimethyl-4-oxocyclohexanecarboxylate (8.9 g, 68% yield; racemic mixture) as a clear yellow oil.

後処理

  1. stirringAfter stirring for 30 min at −40° C.
  2. temperatureto warm to −20° C
  3. stirringAfter stirring for 90 min at −20° C.
  4. customthe mixture was partitioned between more saturated aqueous ammonium chloride and EtOAc
  5. customthe layers were separated
  6. washthe organic material washed sequentially with saturated aqueous ammonium chloride (2×) and brine
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. concentrationthe filtrate was concentrated
  10. dissolutionThe residue was dissolved with DCM, silica gel (39 g)
  11. additionwas added to the solution
  12. customthe volatiles were removed under reduced pressure

出典と根拠

ORDレコード
ord-2518cdf81c8a45e8baf23a2557146831
出典データセット
uspto-grants-2016_06
特許番号
US09365522B2

反応ノート

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